CN110204742A - A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof - Google Patents

A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof Download PDF

Info

Publication number
CN110204742A
CN110204742A CN201910634113.XA CN201910634113A CN110204742A CN 110204742 A CN110204742 A CN 110204742A CN 201910634113 A CN201910634113 A CN 201910634113A CN 110204742 A CN110204742 A CN 110204742A
Authority
CN
China
Prior art keywords
solution
electroresponse
hydrogel
acid
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910634113.XA
Other languages
Chinese (zh)
Inventor
宋文龙
康剑烨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN201910634113.XA priority Critical patent/CN110204742A/en
Publication of CN110204742A publication Critical patent/CN110204742A/en
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/26—Mixtures of macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/52—Hydrogels or hydrocolloids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/36—Amides or imides
    • C08F122/38—Amides
    • C08F122/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/10—Materials for lubricating medical devices
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/16—Materials or treatment for tissue regeneration for reconstruction of eye parts, e.g. intraocular lens, cornea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/24—Homopolymers or copolymers of amides or imides
    • C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00—Characterised by the use of proteins; Derivatives thereof

Abstract

A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof, belongs to electroresponse lubricating hydrogel preparation technical field.The present invention is to introduce the supramolecular system of electroresponse in high-intensitive hydrogel, high intensity hydrogel is because of its porous structure with good mechanical strength and material itself, while giving mechanics of materials support, liquid and ion are moved freely in three-dimensional network；Gel-sol transition can occur during applying external electric field for electroresponse Supramolecular Network, form liquid layer on surface in the form of colloidal sol after de-assembly, significantly reduce the coefficient of friction of material surface；The material surface after de-assembly is changed due to the appearance transmitance of liquid layer simultaneously.Cornea intelligent aqueous gel is imitated in the electroresponse that this patent proposes, is expected to be applied to artificial cornea substitute；The present invention can form hydrogel using one kettle way heating water bath in a short time, have certain application potential in large-scale industrial production and biomedical simulation field.

Description

A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof
Technical field
The invention belongs to electroresponse lubricating hydrogel preparation technical fields, and in particular to a kind of high intensity electricity of imitative cornea Respond lubricating hydrogel and preparation method thereof.
Background technique
Important component of the cornea as eyes has good mechanical performance and lubricity；The tear when eyes are dry and astringent Gland can secrete tear lubrication cornea, while it has the good transparency again.Therefore integrated many multi-functional manually imitative cornea materials Expect the extensive concern by researcher.Hydrogel is due to its moisture rich in, high transparency and various controllable Performance, it is considered to be the preferred material of imitative cornea.Especially high-intensitive double-network hydrogel is because it is with good mechanical strength Allow liquid and ion in three-dimensional network while giving mechanics of materials support with the porous structure of material itself It moves freely, therefore how to design preparation while keeping hydrogel material excellent mechanical performances, and be able to achieve transmission and profit The control of slip energy reforms into imitative corneal material and faces huge challenge.Electroresponse supramolecular hydrogel is in the mistake for applying external electric field Gel-sol transition occurs for Cheng Zhonghui, and the regulation that colloidal sol is material surface greasy property and photopermeability energy is formed after de-assembly Provide for possibility.Therefore electroresponse supramolecular system and high-strength polymer system are organically combined, makes it in electric field action Under divide sol-gel conversion to forming liquid lubricant layer in hydrogel surface generating unit, significantly reduce the friction system of material surface Several and material transparent degree is to realize the simulation to human eye functions.
Summary of the invention
The object of the present invention is to provide high-intensitive electroresponse lubricating hydrogels of a kind of imitative cornea and preparation method thereof.It should Method is the introducing electroresponse Supramolecular Network in traditional high intensity hydrogel；Polymer covalent provides the skeleton of rigidity To reach enough mechanical support effects, while it allows liquid and ion in three-dimensional network with three-dimensional porous structure In move freely；Gel-sol phase-state change occurs under electric field action for the non-covalent network of supermolecule, so that material is macroscopically The solid-liquid conversion that part occurs forms liquid layer in hydrogel surface, to realize the regulation of surface lubrication, reduces friction system Number；The presence of liquid layer changes the transparency of material simultaneously, achievees the purpose that analog cornea to light through control.What this patent proposed Cornea intelligent aqueous gel is imitated in electroresponse, is expected to be applied to artificial cornea substitute；Meanwhile this method is easy to operate, using one Pot method heating water bath can form hydrogel in a short time, have one in large-scale industrial production and biomedical simulation field Fixed application potential.
A kind of preparation method of the high-intensitive electroresponse lubricating hydrogel of imitative cornea of the present invention, step is such as Under:
(1) it weighs 5~20g monomer 1 to be added in high purity water, 12~48h is stirred at 75~95 DEG C keeps solid powder complete Fully dissolved；Solution is cooled to room temperature after dissolution, obtaining 1 concentration of monomer is 0.02~2g/mL clear transparent solutions；To above-mentioned molten Monomer 2 is added in liquid, makes its final concentration of 0.01~3g/mL；Then be added crosslinking agent 4, crosslinking agent final concentration of 0.05~ 20mg/mL, 5~20min of stirring are uniformly mixed it；
(2) 0.3~30g natrium carbonicum calcinatum is weighed, be added in 0.1~10L high purity water and is boiled；To the sodium carbonate boiled 1~100g silk is added in solution or the spider's thread 20~40min of degumming, silk or the spider's thread after degumming are washed with deionized dry Only；It repeats scouring processes 1~3 time；Silk or the spider's thread after degumming is in the dry 3~12h of 20~100 DEG C of degree, by the silkworm after drying Silk or the spider's thread are dissolved in the lithium-bromide solution or molar ratio 1 of 9~10mol/L of concentration in the ratio of 1g: 4~10mL solution: In the calcium chloride of 2:8-alcohol-water ternary solution, 60~90 DEG C of solution temperature, 1~12h of dissolution time；By dissolved silk Or spider's thread solution in the dialysis bag of molecular cut off 3500~14000 at 4 DEG C dialyse 2~3d, obtain 1~9wt.%'s of concentration Silk or spider's thread solution；
(3) 2~400mg monomer, 3 or 0.1~10mL step (2) are added thereto in the solution 40mL for taking step (1) to configure Obtained silk or spider's thread solution, stirring 1~3h under the conditions of 20~80 DEG C dissolves monomer；Solution is cooled to room after dissolution Temperature obtains the solution that 3 concentration of monomer is 0.05~50mg/mL；Crosslinking agent 5 is sequentially added into the solution, or adjusts pH=2 ~4, ethyl alcohol (1mL solution adds 1~5 drop ethyl alcohol) or ultrasonic treatment is either added；Final concentration of 0.05~20mg/ of crosslinking agent mL；Initiator 6 is added, final concentration of 0.05~20mg/mL of initiator, then 1~3h of stirring makes solid at room temperature Dissolution；By above-mentioned solution under the conditions of 40~80 DEG C heating water bath 3~for 24 hours, obtain the high-strength of imitative cornea of the present invention Electroresponse lubricating hydrogel is spent, is placed in climatic chamber and saves at room temperature.
Monomer 1 and monomer 2 in above-mentioned steps (1) obtain high intensity hydrogel material after reacting, and wherein monomer 1 specifically wraps Include: (acrylamide and its derivative can be acrylamide, N,N-DMAA, N- for acrylamide and its derivative N-isopropylacrylamide or hydroxyethyl acrylamide), polyvinyl alcohol, (polysaccharide can be chitosan, agarose, alginic acid to polysaccharide Sodium, Sodium Hyaluronate, cellulose, bacteria cellulose, chondroitin sulfate, metering system chondroitinesulphuric acid), sodium alginate-two Silica, sodium acrylate, ethylene benzotriazole, acryloyl glycine amide, polyethylene glycol diacrylate rouge, urea, gathers silica (2-acrylamido-2-methyl-1-propanesulfonic acid), poly- (2,2- disulfonyl base -4,4- benzidine terephthalamide), poly- second two Alcohol, four arm polyethylene glycol, polyacrylic acid, 2,2,2- trifluoroethyl acrylate, polymethylacrylic acid 2- hydroxyl ethyl ester, gelatin, glue Original, gellan gum, carragheen, 2- phenoxyethyl acrylate, Polyurethane, dodecyl glyceryl itaconate, α-ring paste Essence, beta-cyclodextrin, N- acryloyl glycine amide, polyethyleneglycol diacrylate；Monomer 2 specifically includes: acrylamide and its spreading out (acrylamide and its derivative can be acrylamide, N,N-DMAA, n-isopropyl acrylamide or hydroxyl to biology Ethyl acrylamide), polyvinyl alcohol, (polysaccharide can be chitosan, agarose, sodium alginate, Sodium Hyaluronate, fiber to polysaccharide Element, bacteria cellulose, chondroitin sulfate, metering system chondroitinesulphuric acid), sodium alginate-silica, silica, third Olefin(e) acid sodium, ethylene benzotriazole, acryloyl glycine amide, polyethylene glycol diacrylate rouge, urea, poly- (2- acrylamido -2- first Base -1- propane sulfonic acid), poly- (2,2- disulfonyl base -4,4- benzidine terephthalamide), four arm polyethylene glycol, polyacrylic acid, 2, 2,2- trifluoroethyl acrylate, polymethylacrylic acid 2- hydroxyl ethyl ester, gelatin, collagen, gellan gum, carragheen, 2- phenoxy group second Base acrylate, Polyurethane, dodecyl glyceryl itaconate, -2 (methacryl of N- (carboxymethyl)-N, N- dimethyl Oxygroup) ethamine inner salt, polyacrylic acid, carrageenan, lithium magnesium silicate, polyurethane, acrylamide stearic acid；And monomer 1 and monomer 2 It cannot be identical.
Further, the molecular weight of monomer 1 is 2.5~300,000；
Monomer 3 in above-mentioned steps (2) obtains the supermolecular gel material of electroresponse after reacting, and monomer 3 specifically includes: shell Glycan, sodium alginate, dimethylaminoethyl acrylate methyl ammonia ethyl ester, diethyl aminoethyl methacrylate, gelatin methacrylate, N-isopropyl acrylamide, 3- (trimethoxysilyl) propyl methacrylate, α-chitin, polyacrylic acid, poly- 2- Acrylamide-2-methylpro panesulfonic acid, polyhydroxypropyl acrylate, polybutyl methacrylate, poly hydroxy ethyl acrylate, 3- (methacryl ammonia) oxypropyl trimethyl ammonium hexafluorophosphate, poly-ferrocene silane, Sodium Polyacrylate, poly dimethyl allyl Ammonium chloride, poly diallyldimethylammonium chloride, polyacrylic acid fourth rouge, polyvinyl alcohol, polyacrylamide, polyacrylonitrile, polyvinylpyrrolidine Alkanone, polypyrrole, polystyrolsulfon acid, poly- (3,4- ethylenedioxy thiophene), soybean protein, polyvinylsulfonic acid, hyaluronic acid, Poly- (4-vinylpyridine) Bromide of polypropylene glycol, hydrophobic polysoap, N- dodecyl, gathers poly- dimethylamino propyl acrylamide Ethyl oxazole, poly- 2- acrylamide -2- isobutyl group sulfonic acid, phenyl boric acid, carboxymethyl cellulose, carboxymethyl chitosan, it is Prussian blue, N, N- dimethylaminoethyl methyl methacrylate, vinylpyridine；And monomer 1, monomer 2 and monomer 3 cannot be identical.
Crosslinking agent 4 in above-mentioned steps (1) can trigger the polymerization of monomer 1, and crosslinking agent 4 is glutaraldehyde, and Geniposide, N, N- are sub- Bisacrylamide, N,N-dimethylformamide, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, N- hydroxyl Base succinimide, boric acid, epoxychloropropane etc.；
Crosslinking agent 5 and initiator 6 in above-mentioned steps (4) can trigger the polymerization of monomer 2, and crosslinking agent 5 is glutaraldehyde, capital Buddhist nun Flat, N, N- methylene-bisacrylamide, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, N- hydroxysuccinimidyl acyl Imines, boric acid, epoxychloropropane etc.；Initiator 6 is potassium peroxydisulfate, ammonium persulfate, 2-oxoglutaric acid, 2- hydroxyl -1- [4- (2- Hydroxyl-oxethyl) phenyl]-2- methyl-1-acetone etc..
Detailed description of the invention
Fig. 1: the electroresponse of cornea high intensity is imitated for fibroin albumen-polyacrylamide/polyvinyl alcohol in embodiment 1 and lubricates water The optical photograph of gel.As shown, freshly prepared sample out is liquid (figure a) in the initial state, after heating plastic Become gel state (figure b).The optical photograph of imitative cornea high intensity electroresponse lubricating hydrogel in the remaining embodiments and this It is similar.
Fig. 2: fibroin albumen-polyacrylamide/polyvinyl alcohol to prepare in embodiment 1 imitates the electroresponse of cornea high intensity The scanning electron microscope phenogram of gel surface after lubricating hydrogel freezes-drain processing with freeze drier.It can be seen that water in figure Porous structure is presented in gel rubber material surface, and has the structure distribution of like fibrous on hole wall.What is prepared in the remaining embodiments is imitative The scanning electron microscope phenogram of cornea high intensity electroresponse lubricating hydrogel is similar.
Fig. 3: cornea high intensity electroresponse profit is imitated for fibroin albumen-polyacrylamide/polyvinyl alcohol prepared by embodiment 1 Assembling (anode, figure a)-de-assembly (cathode, the scanning electron microscope phenogram of figure b) that water skiing gel occurs under electric field action.From It can be seen that under electric field action in figure, hydrogel de-assembly (cathode, the surface of figure b) side at fibrous web-like, hole almost by It fills up.(anode, a) side change is unobvious for figure, and structure is similar to raw water gel for assembling.The imitative canthus prepared in the remaining embodiments The scanning electron microscope phenogram of film high intensity electroresponse lubricating hydrogel is similar.Operating method: hydrogel is clipped in two panels Among platinum electrode, cathode (de-assembly), anode (assembling) side hydrogel of 1mm thickness are cut after energization 5min with blade respectively, freeze Metal spraying 6 times after dry.Use HITACHI-SU8020 sem test.
Note: de-assembly process are as follows: the fibroin albumen of hydrogel near surface part is converted under electric field action by gel state Dissolved colloidal state forms liquid layer on surface.Assembling process are as follows: the fibroin albumen of collosol state is converted into gel state under electric field action (this process can only occur in solution state, therefore without phenomenon under the conditions of this).
Fig. 4: fibroin albumen-polyacrylamide/polyvinyl alcohol to prepare in embodiment 1 imitates the electroresponse of cornea high intensity The rupture strength curve figure of lubricating hydrogel.Under electric field action, de-assembly (cathode) partially due to fibroin albumen in hydrogel Internal de-assembly, porous structure collapsing cause mechanical strength to decline.Assembling (anode) partially change it is unobvious, due to network internal A part of water electrolysis, structure slightly change, and intensity slightly declines.The imitative cornea high intensity electroresponse prepared in the remaining embodiments The mechanical strength trend of lubricating hydrogel is similar.Operating method: hydrogel is clipped among two panels platinum electrode, is powered The cathode and anode side hydrogel for cutting 1mm thickness after 5min with blade respectively carries out fracture experiment using ITW-5944 universal testing machine Test.
Fig. 5: fibroin albumen-polyacrylamide/polyvinyl alcohol to prepare in embodiment 1 imitates the electroresponse of cornea high intensity The coefficient of friction figure (swelling) of lubricating hydrogel.Under electric field action, de-assembly (cathode) part fibroin albumen de-assembly, in table Face forms lubricant layer, frictional decrease.The imitative cornea high intensity electroresponse lubricating hydrogel prepared in the remaining embodiments Mechanical strength trend is similar.Operating method: hydrogel is clipped among two panels platinum electrode, after energization 5min, in cathode Surface probe test, result are that de-assembly surveys coefficient of friction；Hydrogel is inverted afterwards, in anode surface probe test, knot Fruit is that coefficient of friction is surveyed in assembling.Test equipment is Tribometer-UMT-2 fretting wear instrument, and probe is Al2O3, diameter 6mm.
Fig. 6: fibroin albumen-polyacrylamide/polyvinyl alcohol to prepare in embodiment 1 imitates the electroresponse of cornea high intensity Lubricating hydrogel transmitance schematic diagram.Composite hydrogel after de-assembly surveys transmitance to be had compared to the composite hydrogel not responded Risen.Operating method: hydrogel is clipped among two panels platinum electrode, purple using Shimadzu UV-3600 after energization 5min The ultraviolet permeability of outer visible near-infrared spectrophotometric measurement de-assembly (cathode) side.
Specific embodiment
Below with reference to embodiment is implemented, the present invention is further elaborated, rather than to be limited with this present invention System.
Embodiment 1
3g natrium carbonicum calcinatum is weighed, be added in 1L water and is boiled.10g natural silk degumming is added in the sodium carbonate liquor boiled 20min, the silk after degumming are washed with deionized completely；It repeats scouring processes 2 times.Take off the silk drying at room temperature 12h of glue. Silk (about 7g) after drying is dissolved in the lithium-bromide solution of 10mol/L (bath raio 1:7), and 65 DEG C of solution temperature, dissolution time 4h.Dissolved silk solution 4 DEG C of dialysis 3d in the dialysis bag of molecular cut off 12000；Solution after dialysis is concentration The silk fibroin protein solution of 5wt.%.
Weigh 5g polyvinyl alcohol (MnTen thousand), 50mL high purity water is added in ≈ 13,95 DEG C of heating stirring 48h keep solid powder molten Solution, is cooled to room temperature by solution after dissolution；Acrylamide 42.63g is added into above-mentioned solution, it is total to solution to add high purity water Volume is 200mL；Then 880 μ L are added, the glutaraldehyde that mass fraction is 50%, stirring 5min is uniformly mixed solution.
Above-mentioned solution 20mL is taken, 1mL silk fibroin protein solution is added, mixed solution is uniformly mixed, and is successively added thereto Enter crosslinking agent N, N- methylene-bisacrylamide 9.25mg, initiator potassium persulfate 16.25mg；Then 30min, which is stirred at room temperature, to be made Solid dissolution；PH=3 is adjusted, complete solution is dissolved and is added in orifice plate, ParafilmTM edge prevents moisture loss, 65 Heating water bath 4h plastic under the conditions of DEG C；Obtained hydrogel is imitative cornea high intensity electroresponse lubrication water of the present invention Gel rubber material, which is placed in climatic chamber saves at room temperature.
The high intensity hydrogel material that the present embodiment uses is polyvinyl alcohol/polyacrylamide；The electroresponse used surpasses Molecular gel material is fibroin albumen.
Embodiment 2
3g natrium carbonicum calcinatum is weighed, be added in 1L water and is boiled.10g natural silk degumming is added in the sodium carbonate liquor boiled 20min, the silk after degumming are washed with deionized completely；It repeats scouring processes 2 times.Take off the silk drying at room temperature 12h of glue. Silk (about 7g) after drying is dissolved in the lithium-bromide solution of 10mol/L 65 DEG C of (bath raio 1:7) solution temperature, dissolution time 4h.Dissolved silk solution 4 DEG C of dialysis 3d in the dialysis bag of molecular cut off 12000；Solution after dialysis is concentration The silk fibroin protein solution of 5wt.%.
2- acrylamide-2-methylpro panesulfonic acid 20.72g is weighed, is dissolved in 100mL high purity water, N, N- methylene is added This mixed solution stirring and dissolving is led to nitrogen and is bubbled 30min, to remove by bisacrylamide 0.62g, a-KG 0.015g Remove oxygen.It polymerize to form poly- 2- acrylamide-2-methylpro panesulfonic acid hydrogel with ultraviolet lamp (wavelength 365nm) irradiation 6h.
N,N-DMAA 29.74g is weighed, 100mL high purity water is dissolved in, crosslinking agent N is then added into solution, N- methylene-bisacrylamide 0.046g, initiator potassium persulfate 0.081g, 1mL silk fibroin protein solution, then in room temperature condition Lower stirring 1h dissolves solid.The poly- 2- acrylamide-2-methylpro panesulfonic acid hydrogel prepared is taken, above-mentioned mixing is soaked into Then 1~2d of solution obtains electro-response hydrogel in 65 DEG C of reaction 6h to swelling equilibrium.The hydrogel is soaked into deionized water It 1 week, changes daily water 4 times, to remove unreacted substance.
The high intensity hydrogel material that the present embodiment uses is poly- 2- acrylamide-2-methylpro panesulfonic acid/poly- N, N- bis- Methacrylamide；The supermolecular gel material of the electroresponse used is fibroin albumen.
Embodiment 3
3g natrium carbonicum calcinatum is weighed, be added in 1L water and is boiled.10g natural silk degumming is added in the sodium carbonate liquor boiled 20min, the silk after degumming are washed with deionized completely；It repeats scouring processes 2 times.Take off the silk drying at room temperature 12h of glue. Silk (about 7g) after drying is dissolved in the lithium-bromide solution of 10mol/L 65 DEG C of (bath raio 1:7) solution temperature, dissolution time 4h.Dissolved silk solution 4 DEG C of dialysis 3d in the dialysis bag of molecular cut off 12000；Solution after dialysis is concentration The silk fibroin protein solution of 5wt.%.
2- acrylamide-2-methylpro panesulfonic acid 20.72g is weighed, is dissolved in 100mL high purity water, N, N- methylene is added This mixed solution stirring and dissolving is led to nitrogen and is bubbled 30min, to remove by bisacrylamide 0.62g, a-KG 0.015g Remove oxygen.It polymerize to form poly- 2- acrylamide-2-methylpro panesulfonic acid hydrogel with ultraviolet lamp (wavelength 365nm) irradiation 6h.
Acrylamide 21.33g is weighed, 100mL high purity water is dissolved in, crosslinking agent N, N- di-2-ethylhexylphosphine oxide are then added into solution Acrylamide 0.046g, initiator potassium persulfate 0.081g, 1mL silk fibroin protein solution, then stirring 1h makes at room temperature Solid dissolution takes.Take the poly- 2- acrylamide-2-methylpro panesulfonic acid hydrogel prepared, be soaked into above-mentioned mixed solution 1~ Then 2d obtains electro-response hydrogel in 65 DEG C of reaction 6h to swelling equilibrium.The hydrogel is soaked into deionized water 1 week, often It is changed water 4 times, to remove unreacted substance.
The high intensity hydrogel material that the present embodiment uses is poly- 2- acrylamide-2-methylpro panesulfonic acid/polyacrylamide Amine；The supermolecular gel material of the electroresponse used is fibroin albumen.
Embodiment 4
3g natrium carbonicum calcinatum is weighed, be added in 1L water and is boiled.10g natural silk degumming is added in the sodium carbonate liquor boiled 20min, the silk after degumming are washed with deionized completely；It repeats scouring processes 2 times.Take off the silk drying at room temperature 12h of glue. Silk (about 7g) after drying is dissolved in the lithium-bromide solution of 10mol/L 65 DEG C of (bath raio 1:7) solution temperature, dissolution time 4h.Dissolved silk solution 4 DEG C of dialysis 3d in the dialysis bag of molecular cut off 12000；Solution after dialysis is concentration The silk fibroin protein solution of 5wt.%.
2- acrylamide-2-methylpro panesulfonic acid sodium 22.93g is weighed, is dissolved in 100mL high purity water, N, N- methylene is added This mixed solution stirring and dissolving is led to nitrogen and is bubbled 30min by base bisacrylamide 0.62g, a-KG 0.015g, with Remove oxygen.Ultraviolet lamp (wavelength 365nm) irradiation 6h polymerize to form poly- 2- acrylamide-2-methylpro panesulfonic acid sodium hydrogel.
N,N-DMAA 29.74g is weighed, 100mL high purity water is dissolved in, crosslinking agent N is then added into solution, N- methylene-bisacrylamide 0.046g, initiator potassium persulfate 0.081g, 1mL silk fibroin protein solution, then in room temperature condition Lower stirring 1h dissolves solid, adjusts pH=3.The poly- 2- acrylamide-2-methylpro panesulfonic acid hydrogel prepared is taken, is impregnated Enter above-mentioned 1~2d of mixed solution to swelling equilibrium, then obtains electro-response hydrogel in 65 DEG C of reaction 6h.The hydrogel is soaked into 1 week in deionized water, change daily water 4 times, to remove unreacted substance.
The high intensity hydrogel material that the present embodiment uses is poly- 2- acrylamide-2-methylpro panesulfonic acid sodium/poly- N, N- Dimethylacrylamide；The supermolecular gel material of the electroresponse used is fibroin albumen.
Embodiment 5
3g natrium carbonicum calcinatum is weighed, be added in 1L water and is boiled.10g natural silk degumming is added in the sodium carbonate liquor boiled 20min, the silk after degumming are washed with deionized completely；It repeats scouring processes 2 times.Take off the silk drying at room temperature 12h of glue. Silk (about 7g) after drying is dissolved in the lithium-bromide solution of 10mol/L 65 DEG C of (bath raio 1:7) solution temperature, dissolution time 4h.Dissolved silk solution 4 DEG C of dialysis 3d in the dialysis bag of molecular cut off 12000；Solution after dialysis is concentration The silk fibroin protein solution of 5wt.%.
2- acrylamide-2-methylpro panesulfonic acid sodium 22.93g is weighed, is dissolved in 100mL high purity water, N, N- methylene is added This mixed solution stirring and dissolving is led to nitrogen and is bubbled 30min by base bisacrylamide 0.62g, a-KG 0.015g, with Remove oxygen.Ultraviolet lamp (wavelength 365nm) irradiation 6h polymerize to form poly- 2- acrylamide-2-methylpro panesulfonic acid sodium hydrogel.
Acrylamide 21.33g is weighed, 100mL high purity water is dissolved in, crosslinking agent N, N- di-2-ethylhexylphosphine oxide are then added into solution Acrylamide 0.046g, initiator potassium persulfate 0.081g, 1mL silk fibroin protein solution, then stirring 1h makes at room temperature Solid dissolution, adjusts pH=3.The poly- 2- acrylamide-2-methylpro panesulfonic acid hydrogel prepared is taken, above-mentioned mixing is soaked into Then 1~2d of solution obtains electro-response hydrogel in 65 DEG C of reaction 6h to swelling equilibrium.The hydrogel is soaked into deionized water It 1 week, changes daily water 4 times, to remove unreacted substance.
The high intensity hydrogel material that the present embodiment uses is poly- 2- acrylamide-2-methylpro panesulfonic acid sodium/polypropylene Amide；The supermolecular gel material of the electroresponse used is fibroin albumen.
Embodiment 6
Weigh 5g polyvinyl alcohol (MnTen thousand), 50mL high purity water is added in ≈ 13,95 DEG C of heating stirring 48h keep solid powder molten Solution, is cooled to room temperature by solution after dissolution；Acrylamide 42.63g is added into above-mentioned solution, it is total to solution to add high purity water Volume is 200mL；Then 880 μ L are added, the glutaraldehyde that mass fraction is 50%, stirring 5min is uniformly mixed solution.
Above-mentioned solution 40mL is taken, 80mg sodium alginate powder is added, 40mg calcium carbonate powder stirs solid powder to molten Solution；Obtain the sodium alginate-Ca that concentration is 2mg/mL2+Solution；Crosslinking agent N, N- di-2-ethylhexylphosphine oxide third are sequentially added into the solution Initiator potassium persulfate 32.5mg is added in acrylamide 18.5mg；Then stirring 1h dissolves solid at room temperature；It has dissolved Full solution is added in corresponding mold, and tightly wrapping edge with sealed membrane prevents moisture from evaporating, heating water bath under the conditions of 65 DEG C 4h plastic；Obtained hydrogel is imitative cornea high intensity electroresponse lubricating hydrogel material of the present invention, the sample It is placed in climatic chamber and saves at room temperature.
The high intensity hydrogel material that the present embodiment uses is polyvinyl alcohol/polyacrylamide；The electroresponse used surpasses Molecular gel material is sodium alginate-Ca2+System.
Embodiment 7
Weigh 5g polyvinyl alcohol (MnTen thousand), 50mL high purity water is added in ≈ 13,95 DEG C of heating stirring 48h keep solid powder molten Solution, is cooled to room temperature by solution after dissolution；Acrylamide 42.63g is added into above-mentioned solution, it is total to solution to add high purity water Volume is 200mL；Then 880 μ L are added, the glutaraldehyde that mass fraction is 50%, stirring 5min is uniformly mixed solution.
Take above-mentioned solution 40mL, be added dissolved in advance chitosan solution (80mg chitosan, 10mL ultrapure water, slowly The solution that 2mol/L hydrochloric acid is uniformly mixed so as to obtain concentration to pH=5.6) as 1.6mg/mL is added；Crosslinking agent is sequentially added into the solution Initiator potassium persulfate 32.5mg is added in N, N- methylene-bisacrylamide 18.5mg；；Then stirring 1h makes at room temperature Solid dissolution；It dissolves complete solution to be added in corresponding mold, tightly wrapping edge with sealed membrane prevents moisture from evaporating, at 65 DEG C Under the conditions of heating water bath 4h plastic；Obtained hydrogel is imitative cornea high intensity electroresponse lubrication water-setting of the present invention Glue material, which is placed in climatic chamber saves at room temperature.
The high intensity hydrogel material that the present embodiment uses is polyvinyl alcohol/polyacrylamide；The electroresponse used surpasses Molecular gel material is chitosan.
Embodiment 8
2.60g diethyl aminoethyl methacrylate is weighed, the stirring of 4mL high purity water is added, obtains muddy solution.? 1g acrylic acid is added dropwise in solution, until solution is clarified.Then, 0.78g acrylamide is added in solution under stiring.Logical nitrogen At least 30min blister to remove oxygen.Then, the ammonium persulfate aqueous solution of 0.5ml is added as initiator.
Weigh 5g polyvinyl alcohol (MnTen thousand), 50mL high purity water is added in ≈ 13,95 DEG C of heating stirring 48h keep solid powder molten Solution, is cooled to room temperature by solution after dissolution；Acrylamide 42.63g is added into above-mentioned solution, it is total to solution to add high purity water Volume is 200mL；Then 880 μ L are added, the glutaraldehyde that mass fraction is 50%, stirring 5min is uniformly mixed solution.
Above-mentioned solution 40mL is taken, the diethyl aminoethyl methacrylate precursor solution that 1mL is prepared, mixed solution is added After slight oscillatory mixes, crosslinking agent N, N- methylene-bisacrylamide 18.5mg are sequentially added into the solution, are added and are caused Agent potassium peroxydisulfate 32.5mg；Then stirring 1h dissolves solid at room temperature；Complete solution is dissolved to be added to accordingly In mold, tightly wrapping edge with sealed membrane prevents moisture from evaporating, heating water bath 4h plastic under the conditions of 65 DEG C；Obtained hydrogel is i.e. For imitative cornea high intensity electroresponse lubricating hydrogel material of the present invention, which is placed in climatic chamber in room temperature Under the conditions of save.
The high intensity hydrogel material that the present embodiment uses is polyvinyl alcohol/polyacrylamide；The electroresponse used surpasses Molecular gel material is diethyl aminoethyl methacrylate.
Embodiment 9
2.60g dimethylaminoethyl acrylate methyl ammonia ethyl ester is weighed, the stirring of 4mL high purity water is added, obtains muddy solution.In solution Middle dropwise addition 1g acrylic acid, until solution is clarified.Then, 0.78g acrylamide is added in solution under stiring.Logical nitrogen blistering At least 30min is to remove oxygen.Then, the ammonium persulfate aqueous solution of 0.5ml is added, 0.25ml phosphate buffer solution is as oxidation Restore initiator.
Weigh 5g polyvinyl alcohol (MnTen thousand), 50mL high purity water is added in ≈ 13,95 DEG C of heating stirring 48h keep solid powder molten Solution, is cooled to room temperature by solution after dissolution；Acrylamide 42.63g is added into above-mentioned solution, it is total to solution to add high purity water Volume is 200mL；Then 880 μ L are added, the glutaraldehyde that mass fraction is 50%, stirring 5min is uniformly mixed solution.
Above-mentioned solution 40mL is taken, the dimethylaminoethyl acrylate methyl ammonia ethyl ester precursor solution that 1mL is prepared is added, mixed solution is through light After micro oscillation mixes, crosslinking agent N, N- methylene-bisacrylamide 18.5mg are sequentially added into the solution, and initiator mistake is added Potassium sulfate 32.5mg；Then stirring 1h dissolves solid at room temperature；It dissolves complete solution and is added to corresponding mold In, tightly wrapping edge with sealed membrane prevents moisture from evaporating, heating water bath 4h plastic under the conditions of 65 DEG C；Obtained hydrogel is this The invention imitative cornea high intensity electroresponse lubricating hydrogel material, the sample are placed in climatic chamber in room temperature condition Lower preservation.
The high intensity hydrogel material that the present embodiment uses is polyvinyl alcohol/polyacrylamide；The electroresponse used surpasses Molecular gel material is dimethylaminoethyl acrylate methyl ammonia ethyl ester.

Claims (7)

1. a kind of preparation method of the high-intensitive electroresponse lubricating hydrogel of imitative cornea, its step are as follows:
(1) it weighs 5~20g monomer 1 to be added in high purity water, 12~48h is stirred at 75~95 DEG C keeps solid powder completely molten Solution；Solution is cooled to room temperature after dissolution, obtaining 1 concentration of monomer is 0.02~2g/mL clear transparent solutions；Into above-mentioned solution Monomer 2 is added, makes its final concentration of 0.01~3g/mL；Then crosslinking agent 4, final concentration of 0.05~20mg/ of crosslinking agent is added ML, 5~20min of stirring are uniformly mixed it；
(2) 0.3~30g natrium carbonicum calcinatum is weighed, be added in 0.1~10L high purity water and is boiled；To the sodium carbonate liquor boiled Middle addition 1~100g silk or the spider's thread 20~40min of degumming, silk or the spider's thread after degumming are washed with deionized completely；Weight Multiple scouring processes 1~3 time；Silk or the spider's thread after degumming in the dry 3~12h of 20~100 DEG C of degree, by after drying silk or spider Silk is dissolved in the lithium-bromide solution of 9~10mol/L of concentration or the chlorine of molar ratio 1:2:8 in the ratio of 1g: 4~10mL solution Change in calcium-alcohol-water ternary solution, 60~90 DEG C of solution temperature, 1~12h of dissolution time；Dissolved silk or the spider's thread is molten Liquid in the dialysis bag of molecular cut off 3500~14000 at 4 DEG C dialyse 2~3d, obtain silk or the spider of 1~9wt.% of concentration Silk solution；
(3) 2~400mg monomer, 3 or 0.1~10mL step (2) are added thereto and obtain by the solution 40mL for taking step (1) to configure Silk or spider's thread solution, under the conditions of 20~80 DEG C stir 1~3h dissolve monomer；Solution is cooled to room temperature after dissolution, Obtain the solution that 3 concentration of monomer is 0.05~50mg/mL；Sequentially add crosslinking agent 5 into the solution, or adjust pH=2~ 4, ethyl alcohol (1mL solution adds 1~5 drop ethyl alcohol) or ultrasonic treatment is either added；Final concentration of 0.05~20mg/ of crosslinking agent mL；Initiator 6 is added, final concentration of 0.05~20mg/mL of initiator, then 1~3h of stirring makes solid at room temperature Dissolution；By above-mentioned solution under the conditions of 40~80 DEG C heating water bath 3~for 24 hours, obtain the high-strength of imitative cornea of the present invention Electroresponse lubricating hydrogel is spent, is placed in climatic chamber and saves at room temperature.
Monomer 1 are as follows: acrylamide and its derivative, polyvinyl alcohol, polysaccharide, sodium alginate-silica, silica, propylene Sour sodium, ethylene benzotriazole, acryloyl glycine amide, polyethylene glycol diacrylate rouge, urea, poly- (2- acrylamido -2- first Base -1- propane sulfonic acid), poly- (2,2- disulfonyl base -4,4- benzidine terephthalamide), polyethylene glycol, four arm polyethylene glycol, poly- Acrylic acid, 2,2,2- trifluoroethyl acrylate, polymethylacrylic acid 2- hydroxyl ethyl ester, gelatin, collagen, gellan gum, carragheen, 2- Phenoxyethyl acrylate, Polyurethane, dodecyl glyceryl itaconate, alpha-cyclodextrin, beta-cyclodextrin, N- acryloyl Glycine amide, polyethyleneglycol diacrylate；
Monomer 2 is acrylamide and its derivative, polyvinyl alcohol, polysaccharide, sodium alginate-silica, silica, acrylic acid Sodium, ethylene benzotriazole, acryloyl glycine amide, polyethylene glycol diacrylate rouge, urea, poly- (2- acrylamido -2- methyl - 1- propane sulfonic acid), poly- (2,2- disulfonyl base -4,4- benzidine terephthalamide), four arm polyethylene glycol, polyacrylic acid, 2,2, 2- trifluoroethyl acrylate, polymethylacrylic acid 2- hydroxyl ethyl ester, gelatin, collagen, gellan gum, carragheen, 2- Phenoxyethyl Acrylate, Polyurethane, dodecyl glyceryl itaconate, -2 (methacryloxypropyl of N- (carboxymethyl)-N, N- dimethyl Base) ethamine inner salt, polyacrylic acid, carrageenan, lithium magnesium silicate, polyurethane, acrylamide stearic acid；
Monomer 3 is chitosan, sodium alginate, dimethylaminoethyl acrylate methyl ammonia ethyl ester, diethyl aminoethyl methacrylate, gelatin Methacrylate, n-isopropyl acrylamide, 3- (trimethoxysilyl) propyl methacrylate, α-chitin, Polyacrylic acid, poly- 2- acrylamide-2-methylpro panesulfonic acid, polyhydroxypropyl acrylate, polybutyl methacrylate, poly- methyl Hydroxy-ethyl acrylate, 3- (methacryl ammonia) oxypropyl trimethyl ammonium hexafluorophosphate, poly-ferrocene silane, Sodium Polyacrylate, Polydimethyl diallyl ammonium chloride, poly diallyldimethylammonium chloride, polyacrylic acid fourth rouge, polyvinyl alcohol, polyacrylamide, polypropylene Nitrile, polyvinylpyrrolidone, polypyrrole, polystyrolsulfon acid, poly- (3,4- ethylenedioxy thiophene), soybean protein, polyethylene Poly- (4-vinylpyridine) Bromide of base sulfonic acid, hyaluronic acid, polypropylene glycol, hydrophobic polysoap, N- dodecyl, poly- dimethylamino Propylacrylamide, poly- ethyl oxazole, poly- 2- acrylamide -2- isobutyl group sulfonic acid, phenyl boric acid, carboxymethyl cellulose, carboxymethyl Chitosan, Prussian blue, N, N- dimethylaminoethyl methyl methacrylate, vinylpyridine；
Monomer 1, monomer 2 and monomer 3 cannot be identical.
2. a kind of preparation method of the high-intensitive electroresponse lubricating hydrogel of imitative cornea as described in claim 1, feature Be: the crosslinking agent 4 in step (1) is glutaraldehyde, Geniposide, N, N- methylene bisacrylamide acyl for causing the polymerization of monomer 1 Amine, N,N-dimethylformamide, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, n-hydroxysuccinimide, Boric acid or epoxychloropropane.
3. a kind of preparation method of the high-intensitive electroresponse lubricating hydrogel of imitative cornea as described in claim 1, feature Be: crosslinking agent 5 and initiator 6 in step (4) polymerize for causing monomer 2, and crosslinking agent 5 is glutaraldehyde, Geniposide, N, N- Methylene-bisacrylamide, 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, n-hydroxysuccinimide, boron Acid or epoxychloropropane；Initiator 6 is potassium peroxydisulfate, ammonium persulfate, 2-oxoglutaric acid or 2- hydroxyl -1- [4- (2- '-hydroxyethoxy Base) phenyl]-2- methyl-1-acetone.
4. a kind of preparation method of the high-intensitive electroresponse lubricating hydrogel of imitative cornea as described in claim 1, feature Be: acrylamide and its derivative are acrylamide, N,N-DMAA, n-isopropyl acrylamide or ethoxy Acrylamide.
5. a kind of preparation method of the high-intensitive electroresponse lubricating hydrogel of imitative cornea as described in claim 1, feature Be: polysaccharide is chitosan, agarose, sodium alginate, Sodium Hyaluronate, cellulose, bacteria cellulose, chondroitin sulfate or first Base propylene chondroitinesulphuric acid.
6. a kind of preparation method of the high-intensitive electroresponse lubricating hydrogel of imitative cornea as described in claim 1, feature Be: the molecular weight of monomer 1 is 2.5~300,000.
7. a kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea, it is characterised in that: be by claim 1~6 any one Method described in is prepared.
CN201910634113.XA 2019-07-15 2019-07-15 A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof Pending CN110204742A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910634113.XA CN110204742A (en) 2019-07-15 2019-07-15 A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910634113.XA CN110204742A (en) 2019-07-15 2019-07-15 A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110204742A true CN110204742A (en) 2019-09-06

Family

ID=67797518

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910634113.XA Pending CN110204742A (en) 2019-07-15 2019-07-15 A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110204742A (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110713749A (en) * 2019-10-16 2020-01-21 东南大学 Electric response polymer material and preparation method and application thereof
CN111484634A (en) * 2020-04-27 2020-08-04 哈尔滨工业大学 Self-healing multi-bridged network chitosan-derived hydrogel and preparation method thereof
CN112316219A (en) * 2020-09-29 2021-02-05 浙江大学 Anti-adhesion hydrogel-silk scaffold composite membrane and preparation and application thereof
CN112500507A (en) * 2020-12-02 2021-03-16 瑞希(重庆)生物科技有限公司 Modified polyhydroxyethyl methacrylate gel, preparation method, pharmaceutical excipient and external gel
CN112521564A (en) * 2020-11-14 2021-03-19 中国石油天然气股份有限公司 Microgel enhanced gelatin-PAM double-network hydrogel and preparation method thereof
CN112538136A (en) * 2019-09-20 2021-03-23 天津大学 Solvent-free body gel and preparation method thereof
CN112552432A (en) * 2020-11-14 2021-03-26 中国石油天然气股份有限公司 Active microgel reinforced hydrogel and preparation method thereof
CN113185712A (en) * 2021-03-01 2021-07-30 浙江云上云科技有限公司 Preparation method of composite hydrogel with antiviral effect
CN113372582A (en) * 2021-06-23 2021-09-10 太原理工大学 Bionic composite hydrogel and preparation method and application thereof
CN113461974A (en) * 2021-07-28 2021-10-01 吉林大学 Gas response surface lubricating hydrogel and preparation method thereof
CN113456895A (en) * 2021-07-20 2021-10-01 广州市朴道联信生物科技有限公司 GelMA-collagen double-network antibacterial cornea repair material and preparation method and application thereof
CN113896908A (en) * 2021-10-11 2022-01-07 上海大学 Composite hydrogel and preparation method thereof, thermoelectric dual-drive composite hydrogel intelligent window and preparation method thereof
CN111944094B (en) * 2020-08-07 2022-01-07 西南石油大学 Hydrogel copolymer, oil-water separation coating, preparation method and application of oil-water separation coating, oil-water separation net and preparation method of oil-water separation net
CN114752087A (en) * 2022-04-21 2022-07-15 华南理工大学 Soybean protein isolate-based organic gel and preparation method thereof
CN114763399A (en) * 2021-02-05 2022-07-19 天津大学 Digital light processing 3D printing artificial cornea, printing method and application thereof
CN115591274A (en) * 2022-09-20 2023-01-13 中国海洋大学（Cn） Coupled polymyxin B cryogel for removing endotoxin, preparation method and application thereof
CN115990969A (en) * 2023-03-21 2023-04-21 熹微(苏州)生物医药科技有限公司 Bionic biological material and preparation method thereof
CN115990134A (en) * 2022-11-08 2023-04-21 四川大学华西医院 Injectable hydrogel/nanogel drug-loaded slow-release system and preparation method and application thereof
CN115990134B (en) * 2022-11-08 2024-05-10 四川大学华西医院 Injectable hydrogel/nanogel drug-loaded slow-release system and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006116137A2 (en) * 2005-04-21 2006-11-02 The Board Of Trustees Of The Leland Stanford Junior University Artificial cornea
CN106124587A (en) * 2016-06-21 2016-11-16 苏州艾博迈尔新材料有限公司 A kind of thin film bio electrode
CN107670104A (en) * 2017-11-21 2018-02-09 吉林大学 A kind of preparation method with shearing force-responsive self-lubricating bionic joint cartilage
CN108341973A (en) * 2018-03-22 2018-07-31 吉林大学 A kind of preparation method of high strength ionic response lubricating hydrogel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006116137A2 (en) * 2005-04-21 2006-11-02 The Board Of Trustees Of The Leland Stanford Junior University Artificial cornea
CN106124587A (en) * 2016-06-21 2016-11-16 苏州艾博迈尔新材料有限公司 A kind of thin film bio electrode
CN107670104A (en) * 2017-11-21 2018-02-09 吉林大学 A kind of preparation method with shearing force-responsive self-lubricating bionic joint cartilage
CN108341973A (en) * 2018-03-22 2018-07-31 吉林大学 A kind of preparation method of high strength ionic response lubricating hydrogel

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIN YIAN，ET AL: "Tuning Chemical and Physical Cross-Links in Silk Electrogels for Morphological Analysis and Mechanical Reinforcement", 《BIOMACROMOLECULES》 *
SHI ZHIJUN,ET AL: "Electroconductive natural polymer-based hydrogels", 《BIOMATERIALS》 *

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112538136A (en) * 2019-09-20 2021-03-23 天津大学 Solvent-free body gel and preparation method thereof
CN112538136B (en) * 2019-09-20 2021-10-08 天津大学 High-strength hydrogel and preparation method thereof
CN110713749A (en) * 2019-10-16 2020-01-21 东南大学 Electric response polymer material and preparation method and application thereof
CN110713749B (en) * 2019-10-16 2022-07-29 东南大学 Electric response polymer material and preparation method and application thereof
CN111484634A (en) * 2020-04-27 2020-08-04 哈尔滨工业大学 Self-healing multi-bridged network chitosan-derived hydrogel and preparation method thereof
CN111484634B (en) * 2020-04-27 2022-04-01 哈尔滨工业大学 Self-healing multi-bridged network chitosan-derived hydrogel and preparation method thereof
CN111944094B (en) * 2020-08-07 2022-01-07 西南石油大学 Hydrogel copolymer, oil-water separation coating, preparation method and application of oil-water separation coating, oil-water separation net and preparation method of oil-water separation net
CN112316219B (en) * 2020-09-29 2022-05-10 浙江大学 Anti-adhesion hydrogel-silk scaffold composite membrane and preparation and application thereof
CN112316219A (en) * 2020-09-29 2021-02-05 浙江大学 Anti-adhesion hydrogel-silk scaffold composite membrane and preparation and application thereof
CN112552432B (en) * 2020-11-14 2022-11-04 中国石油天然气股份有限公司 Active microgel reinforced hydrogel and preparation method thereof
CN112552432A (en) * 2020-11-14 2021-03-26 中国石油天然气股份有限公司 Active microgel reinforced hydrogel and preparation method thereof
CN112521564A (en) * 2020-11-14 2021-03-19 中国石油天然气股份有限公司 Microgel enhanced gelatin-PAM double-network hydrogel and preparation method thereof
CN112500507A (en) * 2020-12-02 2021-03-16 瑞希(重庆)生物科技有限公司 Modified polyhydroxyethyl methacrylate gel, preparation method, pharmaceutical excipient and external gel
CN114763399B (en) * 2021-02-05 2023-07-07 天津大学 Digital light processing 3D printing artificial cornea, printing method and application thereof
CN114763399A (en) * 2021-02-05 2022-07-19 天津大学 Digital light processing 3D printing artificial cornea, printing method and application thereof
CN113185712A (en) * 2021-03-01 2021-07-30 浙江云上云科技有限公司 Preparation method of composite hydrogel with antiviral effect
CN113185712B (en) * 2021-03-01 2022-08-23 浙江云上云科技有限公司 Preparation method of composite hydrogel with antiviral effect
CN113372582A (en) * 2021-06-23 2021-09-10 太原理工大学 Bionic composite hydrogel and preparation method and application thereof
CN113456895B (en) * 2021-07-20 2022-05-06 广州市朴道联信生物科技有限公司 GelMA-collagen double-network antibacterial cornea repair material and preparation method and application thereof
CN113456895A (en) * 2021-07-20 2021-10-01 广州市朴道联信生物科技有限公司 GelMA-collagen double-network antibacterial cornea repair material and preparation method and application thereof
CN113461974A (en) * 2021-07-28 2021-10-01 吉林大学 Gas response surface lubricating hydrogel and preparation method thereof
CN113461974B (en) * 2021-07-28 2022-05-17 吉林大学 Gas response surface lubricating hydrogel and preparation method thereof
CN113896908A (en) * 2021-10-11 2022-01-07 上海大学 Composite hydrogel and preparation method thereof, thermoelectric dual-drive composite hydrogel intelligent window and preparation method thereof
CN113896908B (en) * 2021-10-11 2023-06-23 上海大学 Composite hydrogel, preparation method thereof, thermoelectric dual-drive composite hydrogel intelligent window and preparation method thereof
CN114752087A (en) * 2022-04-21 2022-07-15 华南理工大学 Soybean protein isolate-based organic gel and preparation method thereof
CN114752087B (en) * 2022-04-21 2024-03-22 华南理工大学 Soybean protein isolate-based organic gel and preparation method thereof
CN115591274A (en) * 2022-09-20 2023-01-13 中国海洋大学（Cn） Coupled polymyxin B cryogel for removing endotoxin, preparation method and application thereof
CN115990134A (en) * 2022-11-08 2023-04-21 四川大学华西医院 Injectable hydrogel/nanogel drug-loaded slow-release system and preparation method and application thereof
CN115990134B (en) * 2022-11-08 2024-05-10 四川大学华西医院 Injectable hydrogel/nanogel drug-loaded slow-release system and preparation method and application thereof
CN115990969A (en) * 2023-03-21 2023-04-21 熹微(苏州)生物医药科技有限公司 Bionic biological material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN110204742A (en) A kind of high-intensitive electroresponse lubricating hydrogel of imitative cornea and preparation method thereof
CN107236135A (en) A kind of gelatin hydrogel and its preparation method and application
CN109432505B (en) Porous-level composite medical gel scaffold constructed through 3D printing and preparation method thereof
CN107602884B (en) Silk fibroin/chitosan composite intelligent hydrogel and preparation method thereof
CN103467652B (en) A kind of hydrogel contact glass and preparation method thereof
Feng et al. Synthesis and swelling behaviors of yeast-g-poly (acrylic acid) superabsorbent co-polymer
WO2003093337A1 (en) Hydrogel of (semi)interpenetrating network structure and process for producing the same
CN107118359B (en) Photo-curing hydrogel and preparation method thereof
CN110498886A (en) A kind of lubricating hydrogel material and its preparation method and application
CN102888027B (en) Bacterial cellulose/collagen-chitosan composite material and preparation method thereof
WO2020156291A1 (en) Physical and chemical double cross-linked network high-strength gelatin hydrogel and preparation method therefor
WO2012057751A1 (en) Crosslinked cellulosic polymers
CN102850477B (en) Clay-based nano silver composite hydrogel and preparation method thereof
JP2010510347A (en) Porous polymer material with crosslinkable wetting agent
CN106693050B (en) A kind of preparation method of the compound support frame material based on collagen and collagenous fibres
CN109438728A (en) A kind of Thermo-sensitive conductive hydrogel and preparation method thereof of metallic ion coordination effect enhancing
CN109939066A (en) Stimuli responsive hydrogel and its preparation method and application based on functionalization dual network
CN102617787B (en) Hydrogel contact lens material and preparation method thereof
CN106243410A (en) A kind of hydroxyethyl chitosan/hyaluronic acid double-network hydrogel and preparation method thereof
Park et al. Preparation of collagen‐immobilized poly (ethylene glycol)/poly (2‐hydroxyethyl methacrylate) interpenetrating network hydrogels for potential application of artificial cornea
Shaheen et al. Synergistic effect of various metal ions on the mechanical, thixotropic, self-healing, swelling and water retention properties of bimetallic hydrogels of alginate
CN109517193A (en) A kind of carboxyetbyl chitosan/polyvinyl alcohol self-healing hydrogel and its preparation method and application
KR102440646B1 (en) Hydrogel composite comprising gelatin and synthetic polymer, and process for preparing the same
WO2023116060A1 (en) Structured hydrogel, and preparation method for hydrogel heart and valves
CN109251330A (en) Nano-chitosan-PVA hydrogel and its preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination